Epichlorohydrin → HCID 21536094, compound

Participants

Reaction Steps

2-benzyloxy-4-nitrophenyl was iodinated to 2-benzyloxy-6-iodo-4-nitrophenol of melting point 143°C-145°C in the manner described for an analogous compound in J.Am.Chem. Soc. 75 4290 (1953). This compound was converted with epichlorohydrine into 2-(hydroxymethyl)-5-iodo-7-nitro-1,4-benzodioxane by the method described in J.Ned. Chem. 1965 page 455 for an analogous compound. The substance obtained was ethylated to 2-(ethoxymethyl)-5-iodo-7-nitro-1,4-benzodioxane (melting point of the crude product 90°--99°C), and this was converted with CF3J and powdered copper in dimethylformamide into 2-(ethoxymethyl)-7-nitro-5-(trifluoromethyl)-1,4-benzodioxan by the method described in Tetrahedron Letters 1969 pages 4095-4096. The reaction product was hydrogenated by means of a palladium on active carbon catalyst at room temperature and under a pressure of about 1.1 atmospheres to form 7-amino-2-(ethoxymethyl)-5-(trifluoromethyl)-1,4-benzodioxan, which was immediately converted with 2-(ethoxymethylene)malonic acid diethyl ester into 2- { [2-(ethoxymethyl)-5-(trifluromethyl)-1,4-benzodioxan-7-ylamino] -methylene } malonic acid diethyl ester which had a melting point of 96°-98°C.

Provenance & Evidence